JPS58190841A - Composition of coloring agent for glass - Google Patents

Abstract

PURPOSE:To provide a titled compsn. which is produced by kneading specific inorg. mixed powder with an org. solvent, etc. and which forms a transparent and smooth colored part on the surface of a blank material for glass by ion substitution when applied on the surface of the blank material. CONSTITUTION:A compsn. of a coloring agent for glass which is produced by mixing inorg. mixed powder consisting of 20-90pts.wt. CuSO4, 20-90pts.wt. sulfate of an alkali metal, 5-40pts.wt. an inorg. filler (e.g., Al2O3, TiO2, Fe2O3, etc.) and, if necessary, up to 1pt.wt. silver salt (e.g., AgNO3, Ag2SO4, etc.) with >=1 kind selected among an inorg. solvent (e.g., butyl carbitol, acetone, etc.), oil [e.g., high b.p. oil (e.g., pine oil, etc.) or said oil compounded with a thickener (e.g., ethyl cellulose, etc.)] and wax (which is normally solid and assumes a liquid state with slight heating), and which forms a transparent and smooth colored part on the surface of a blank material for glass by ion substitution when applied on the surface of the blank material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a glass colorant composition, specifically a new paste or hot melt colorant composition that can be applied to the surface of a glass material to form a transparent and smooth colored area on the surface of the material through sulfur substitution. The present invention relates to a glass colorant composition.

Currently, Ay2 is the main glass colorant that can be applied to the glass surface to form a colored part through sulfur substitution.
Ishishi compositions of SCu S yarns are known.

The composition is applied to the glass surface by scree printing or the like, then fired, and then the firing residue is removed by washing with water, whereby the surface (inside) of the glass material can be transparently colored, for example, with graduations on a scale such as a female cylinder. It is used for coloring parts, etc. However, since the color is orange, this requires the use of expensive silver (silver sulfide) and has the disadvantage that the coloring obtained is limited to a difficult-to-discernible yellow or ashmber color.

Recently, glass coloring glass using copper salt has been commercially available, but it can only be colored if it is fired in a reducing atmosphere, and the only color that can be obtained is red. .

The present invention uses copper sulfate as the main component instead of the above-mentioned known glass coloring glass, and by baking it under normal atmosphere, it is possible to make transparent glass coloring that is easy to identify, and the composition and firing temperature can be changed slightly. The object of the present invention is to provide a new glass colorant composition that can change the coloring to various tones just by changing the coloring composition.

That is, the present invention uses an inorganic mixed powder consisting of 20 to 90 parts by weight of copper sulfate, 20 to 90 parts by weight of an alkali metal sulfate, 5 to 40 parts by weight of an inorganic filler, and, if necessary, up to 1 part by weight of a silver salt, in an organic solvent and an oil. The present invention relates to a glass colorant composition which is kneaded with at least one selected from waxes and waxes, and is applied to the surface of a glass material to form a transparent and smooth colored portion on the surface of the material through sulfur substitution.

The present inventor is able to provide a composition capable of depicting sulfur by sulfur substitution on the surface of a glass material, and the composition can be changed by applying the composition to the surface of a glass material and then firing it. We have invented a surprising new fact that, depending on the firing temperature, the product exhibits smooth transparent coloring of various tones such as blue, silver, yellow, orange, red, etc., depending on the firing temperature. Therefore, by using the composition of the present invention, it is possible to mark the surface of glass with colored markings such as letters and figures, and to decorate glass products with great ease, clarity, and in various tones.

The glass colorant composition of the present invention requires the use of an inorganic mixed powder having the above-mentioned specific composition. Here, copper sulfate is the main component for the desired coloration reaction due to sulfur substitution, and it is thermally decomposed on the glass surface during firing, and the alkali component in the glass is removed by the dealkalization effect of sulfite, which is a decomposition product. It is thought that this makes it easier to pull out and replace the alkali metal oxide with copper sulfur. In any case, this is 2
If the amount is less than 0 parts by weight, it will be difficult to develop a good color tone. In addition, the upper limit of the amount of copper sulfate is determined in relation to other components, and if it exceeds 90 parts by weight, the amount of other components may be too small compared to the total amount of other components. becomes difficult to play. As the alkali metal sulfate used in combination with the copper sulfate, specifically, lithium sulfate, sodium sulfate, and potassium sulfate can be used alone or in combination of two or more. The 2nd class alkali metal sulfate is 2
When used together in a range of 0 to 90 parts by weight, it becomes a melt on the glass surface together with the copper sulfate, and mainly contributes to improving the adhesion to the surface of the glass material. Displacement can be enhanced. Among the above alkali metal sulfates, sodium sulfate is particularly suitable. Further, it is necessary to blend a predetermined amount of an inorganic filler into the inorganic mixed powder used in the present invention. The inorganic filler, by its blending, contributes to the suitability of the resulting composition for screech printing, especially to the creation of a clear design by the printing, and also prevents shrinkage of the melt during firing after application and improves color development. It also has a cocitrol effect that changes the shade of color. As the filler, various commonly known heat-resistant inorganic substances can be used.

Typical examples thereof include Al-sansu (A1203), Titashi oxide (T Jo 2 ), and Silkoshi (Z r O 2 ).
), zirconium silicate (ZrSi04), rehydrated calcium oxide (CaCO3), iron oxide (Ft203), and the like. Furthermore, a small amount (up to 1 part by weight) of silver salt can be added to the above-mentioned inorganic mixed powder, if necessary, to change the color, which has the advantage of being able to express a wider variety of color tones. Specifically, the silver salts include silver nitrate (AgNO2), silver oxide (Ag2O), silver sulfate (Af2SO4), and silver sulfide (A
t2S), etc.

The above-mentioned inorganic mixed powder can usually be prepared by mixing the compounds belonging to each component in the powder form obtained, but the above-mentioned mixing is usually carried out using a dry method such as Bott-sanru, Ball-sanru, etc. or a wet method (methanol). It is preferable to carry out the process using a pulverizer, and it is also preferable to use a pulverizer to obtain a powder particle size of 1 to 9 num. The above-mentioned particle size guarantees good screech removal and sharpness of the printed design when the resulting composition is applied by screech printing. Accordingly, it can be coated by spray coating, brush painting, 0-lu coater coating, transfer method using transfer paper, etc. In these cases, the above particle size is coarser, for example, about 5.
It may be about 0 μm.

The composition of the present invention is prepared by kneading the inorganic mixed powder prepared as described above with at least one selected from organic solvents, oils, and waxes. Examples of organic solvents include those commonly used in the printing and coating fields, such as butylcalditol, butylcalditol acetate, and other organic solvents; Examples include solvents. The oil may be a high boiling point oil such as Taj Neol or Paij oil, or may be used as a thickener with acrylic resin such as methyl methacrylate resin, butyl methacrylate resin, ethyl heptolose, NidoO cellulose, etc. A combination of cellulose resin, Logiciamici D, and other ODici derivatives can be used. In particular, high-boiling point oils with a combination of so-called resins with good burn resistance, such as the above-mentioned acrylic resins and chill 0-rus resins, and resins with relatively poor burn resistance, such as 0 resistance conductors, are added as thickeners to high boiling point oils. , is suitable, and by its use, the paste obtained will have better adhesion to the glass and the coloring effect of the glass will be more pronounced.

In addition, as the wax, any wax that is solid at normal room temperature, easily melts upon slight heating, and becomes a liquid form suitable for screen printing, etc. can be used. The product is a so-called hot melt type composition.

The blending amounts of the organic solvent, oil, and wax are as follows: 8- The resulting composition is in a liquid form that can be easily applied to the surface of the glass material;
There is no particular limitation as long as it is a paste-like or hot-melt type solid, and of course it can be determined as appropriate depending on the type of compound used, the composition of the inorganic mixed powder, etc. Usually, it is appropriate that the amount is about % to the same weight based on the inorganic mixed powder.

Mixing of the above-mentioned organic solvent, etc. and the inorganic mixed powder can be easily carried out according to the means used for making ordinary stones, for example, by temporarily mixing each component with a sieve machine and then rolling it. .

The composition of the invention thus prepared is applied to a glass material desired to be colored according to conventional methods. For example, paste-like or hot-melt-like materials can be coated with screen printing, and liquid-like materials can be coated with spray paint, 9.0-L coater with a brush, or transfer printing using transfer paper. coated on top.

After coating, the desired transparent and colored glass product can be obtained by firing and washing the surface of the fired glass material with water according to a conventional method. The baking temperature and time at this time differ slightly depending on the composition of the composition of the present invention, the applied film thickness, the type of glass material to which it is applied, etc.

Usually about 500-700°C, preferably 560-65°C
It is appropriate to heat the mixture at a temperature of about 0°C for about 3 to 10 minutes, preferably about 5 minutes.

The composition of the present invention can be prepared as described above from glass substrates used for ordinary glass pullers, bottles, plate glasses, etc. In general, hard glasses (α
-30 to 60X10-7), and furthermore, it is equally applicable to various glassy materials such as lead borosilicate glass, which is known as crystal glass.

The present invention will be explained in more detail below with reference to Examples.

Example 1 Trial view - 115 sulfur oxides R11 (1σ social area - 150 g of g6 sodium chlorate and 50 titanium oxide (T s 02)
F was mixed and pulverized with 1.5 liters of methanol in a pot sanru for 2 days. The slurry taken out was dried and sieved using a +20 mesh sieve to obtain an inorganic mixed powder (average particle size of about 5 μm or less).

100 parts by weight of the above powder was kneaded with 50 parts by weight of oil having the following composition to obtain a glass colorant composition of the present invention in the form of a paste.

<Oil> Paige oil 80% by weight Butylcalditol +01/Ethyl t-O-su 6 〃 0dicium 3:, JD 2 〃Resitish
1. Print the above composition on the tin surface and non-tin surface of a float plate glass using a 250-mesh scratchie, bake at a predetermined temperature for 5 minutes, and then wash with water to remove the baking residue, A glass product colored in the desired transparent color was obtained.

The products obtained had the color tones shown in Table 1 below, depending on the baking temperature.

Table 1 Example 2 100 parts by weight of S-free mixed powder having the same composition as in Example 1 was heated and mixed with 50 parts by weight of wax having the following composition, and then cooled to obtain a hot melt type composition of the present invention. .

<Wax> Higher aliphatic alcohol 75% by weight polyethylene resin 1540 10, // acrylic resin 5 0
8
〃Ethyl cell 0-su 2〃After heating and melting the obtained composition, after printing on the tin surface and non-tin surface of a float plate glass in the same manner as in Example 1,
After firing and washing with water, glass products were obtained which were colored in transparent colors having the same color tones as those shown in Table 1 above, depending on the firing temperature.

Examples 3 to 7 In the same manner as in Example 1, inorganic mixed powders (all having an average particle size of 5 μm or less) having the compositions shown in Table 2 below were obtained.

Table 2 100 parts by weight of each of the above inorganic mixed powders were kneaded with 50 parts by weight of oil having the same composition as used in Example 1 to obtain a paste-like composition of the present invention.

Each of the obtained compositions was screen-printed on Tashizura glass and sheet glass in the same manner as in Example 1, fired, and washed with water. In addition, the colored parts of the colored glass products obtained in each of the above examples were extremely smooth, and especially No distinction was observed at all from the non-colored portion of the glass product except for the color tone, and the boundary line (outline) of the color tone change was very clear and sharp. Furthermore, the screech printability of each composition was extremely good.

(that's all)

Claims (1)

[Claims] ■ 20-90 parts by weight of copper sulfate, 20 parts by weight of alkali metal sulfate
An inorganic mixed powder consisting of ~90 parts by weight, 5 to 40 parts by weight of an inorganic filler, and if necessary up to 1 part by weight of a silver salt is kneaded with at least one selected from organic solvents, oils and waxes, A glass coloring agent composition which is applied to the surface of a glass material to form a transparent and smooth colored area on the surface of the material.